Benzotriazole UV absorbers having enhanced durability

Abstract

Benzotriazole UV absorbers which are substituted at the 5-position of the benzo ring by an electron withdrawing group exhibit enhanced durability and very low loss rates when incorporated into automotive coatings. This is particularly the case when the 3-position of the phenyl ring is also substituted by phenyl or phenylalkyl such as α-cumyl. Compounds where the 5-position of the benzo ring are substituted by perfluoroalkyl such as trifluoromethyl are particularly of interest for both their enhanced durability and for their excellent solubility and excellent color properties in some thermoplastic compositions when the phenyl ring is substituted at the 3-position by hydrogen or tert-alkyl.

What is claimed is:  
     
       1. A composition stabilized against thermal, oxidative or light-induced degradation which comprises 
       (a) an organic material subject to thermal, oxidative or light-induced degradation wherein the organic material is a resin selected from the group consisting of a thermoset acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane modified acrylic melamine, an acrylic resin with carbamate pendant groups crosslinked with melamine or an acrylic polyol resin crosslinked with melamine containing carbamate groups, and  
       (b) an effective stabilizing amount of a compound of formula I, III or IV                    
       wherein 
       G 1  is hydrogen or chloro,  
       G 2  is cyano, perfluoroalkyl of 1 to 12 carbon atoms or fluoro,  
       G 6  is perfluoroalkyl of 1 to 12 carbon atoms,  
       G 7  is hydrogen or perfluoroalkyl of 1 to 12 carbon atoms,  
       E 1  is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms; or E 1  is alkyl of 1 to 24 carbon atoms substituted by one or two hydroxy groups,  
       E 2  and E 2 ′ are independently straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by one to three alkyl of 1 to 4 carbon atoms; or E 2  and E 2 ′ are independently said alkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more —OH, —OCOE 11 , —OE 4 , —NCO, —NH 2 , NHCOE 11 , —NHE 4  or —N(E 4 ) 2 , or mixtures thereof, where E 4  is straight or branched chain alkyl of 1 to 24 carbon atoms; or said alkyl or said alkenyl interrupted by one or more —O—, —NH—or —NE 4 —groups or mixtures thereof and which can be unsubstituted or substituted by one or more —OH, —OE 4  or —NH 2  groups or mixtures thereof;  
       n is 1 or 2,  
       when n is 1, E 5  is OE 6  or NE 7 E 8 , or 
       E 5  is —PO(OE 12 ) 2 , —OSi(E 11 ) 3  or —OCO-E 11 , or straight or branched chain C 1 -C 24 alkyl which is interrupted by —O—, —S—or —NE 11  and which can be unsubstituted or substituted by —OH or —OCO—E 11 , C 5 -C 12  cycloalkyl which is unsubstituted or substituted by —OH, straight chain or branched C 2 -C 18 alkenyl which is unsubstituted or substituted by —OH, C 7 -C 15 aralkyl, —CH 2 —CHOH—E 13  or glycidyl,  
       E 6  is hydrogen, straight or branched chain C 1 -C 24 alkyl which is unsubstituted or substituted by one or more OH, OE 4  or NH 2  groups, or —OE 6  is —(OCH 2 CH 2 ) w OH or —(OCH 2 CH 2 ) w OE 21  where w is 1 to 12 and E 21  is alkyl of 1 to 12 carbon atoms,  
       E 7  and E 8  are independently hydrogen, alkyl of 1 to 18 carbon atoms, straight or branched chain C 3 -C 18 alkyl which is interrupted by —O—, —S—or —NE 11 —, C 5 -C 12 cycloalkyl, C 6 -C 14 aryl or C 1 -C 3 hydroxylalkyl, or E 7  and E 8  together with the N atom are a pyrrolidine, piperidine, piperazine or morpholine ring,  
       E 5  is —X—(Z) p —Y—E 15    
       wherein 
       X is —O—or —N(E 16 )—,  
       Y is —O—or —N(E 17 )—,  
       Z is C 2 -C 12 -alkylene, C 4 -C 12 -alkylene interrupted by one to three nitrogen atoms, oxygen atoms or a mixture thereof, or is C 3 -C 12 -alkylene, butenylene, butynylene, cyclohexylene or phenylene, each substituted by a hydroxyl group,  
       m is zero, 1 or 2,  
       p is 1, or p is also zero when X and Y are —N(E 16 )— and —N(E 17 )—, respectively,  
       E 15  is a group —CO—C(E 18 )═C(H)E 19  or, when Y is —N(E 17 )—, forms together with E 17  a group —CO—CH═CH—CO—, wherein E 18  is hydrogen or methyl, and E 19  is hydrogen, methyl or —CO—X—E 20 , wherein E 20  is hydrogen, C 1 -C 12 -alkyl or a group of the formula                    
       wherein the symbols E 1 , G 2 , X, Z, m and p have the meanings defined above, and E 16  and E 17  independently of one another are hydrogen, C 1 -C 12 -alkyl, C 3 -C 12 -alkyl interrupted by 1 to 3 oxygen atoms, or is cyclohexyl or C 7 -C 15 aralkyl, and E 16  together with E 17  in the case where Z is ethylene, also forms ethylene,  
       when n is 2, E 5  is one of divalent radicals —O—E 9 —O— or —N(E 11 )—E 10 —N(E 11 )—,  
       E 9  is C 2 -C 8 alkylene, C 4 -C 8 alkenylene, C 4 alkenylene, cyclohexylene, straight or branched chain C 4 -C 10 alkylene which is interrupted by —O— or by —CH 2 —CHOH—CH 2 —O—E 14 —O—CH 2 —CHOH—CH 2 —,  
       E 10  being straight or branched chain C 2 -C 12 alkylene which may be interrupted by —O—, cyclohexylene, or                    
       or E 10  and E 11 with the two nitrogen atoms form a piperazine ring, 
       E 14  is straight or branched chain C 2 -C 8 alkylene, straight or branched chain C 4 -C 10 alkylene which is interrupted by —O—, cyclohexylene, arylene or                    
       where E 7  and E 8  are independently hydrogen, alkyl of 1 to 18 carbon atoms or E 7  and E 8  together are alkylene of 4 to 6 carbon atoms, 3-oxapentamethylene, 3-iminopentamethylene or 3-methyliminopentamethylene, 
       E 11  is hydrogen, straight or branched chain C 1 -C 18 alkyl, C 5 -C 12 cycloalkyl, straight or branched chain C 2 -C 18 alkenyl, C 6 -C 14 aryl or C 7 -C 15 aralkyl,  
       E 12  is straight or branched chain C 1 -C 18 alkyl, straight or branched chain C 3 -C 18 alkenyl, C 5 -C 10 cycloalkyl, C 6 -C 16 aryl or C 7 -C 15 aralkyl,  
       E 13  is H, straight chain or branched C 1 -C 18 alkyl which is substituted by —PO(OE 12 ) 2 , phenyl which is unsubstituted or substituted by OH, C 7 -C 15 aralkyl or —CH 2 OE 12 ,  
       L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms, benzylidene, p-xylylene, α,α,α′,α′-tetramethyl-m-xylylene or cycloalkylidene, and  
       with the proviso that when G 2  is —CF 3  and E 1  is hydrogen, E 2  is not methyl.  
     
     
       2. A composition according to  claim 1  wherein the resin is a thermoset acrylic melamine resin or an acrylic urethane resin. 
     
     
       3. A composition according to  claim 1  wherein component (b) is a compound of formula I                    
       wherein 
       G 1  is hydrogen,  
       G 2  is cyano, —CF 3  or fluoro,  
       E 1  is phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms,  
       E 2  is straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms; or E 2  is said alkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more —OH, —OCOE 11 , —OE 4 , —NCO, —NH 2 , —NHCOE 11 , —NHE 4  or —N(E 4 ) 2 , or mixtures thereof, where E 4  is straight or branched chain alkyl of 1 to 24 carbon atoms; or said alkyl or said alkenyl interrupted by one or more —O—, —NH— or —NE 4 — groups or mixtures thereof and which can be unsubstituted or substituted by one or more —OH, —OE 4  or —NH 2  groups or mixtures thereof; or  
       is a compound of formula I wherein, 
       G 1  is hydrogen,  
       G 2  is —CF 3  or fluoro,  
       E 1  is hydrogen or straight or branched alkyl of 4 to 24 carbon atoms, and  
       E 2  is as defined above.  
     
     
       4. A composition according to  claim 1  wherein component (b) is a compound of formula IIIA                    
       wherein 
       G 1  is hydrogen,  
       G 2  is —CF 3  or fluoro,  
       E 1  is hydrogen, straight or branched alkyl of 4 to 24 carbon atoms or phenylalkyl of 7 to 15 carbon atoms,  
       E 5  is —OE 6  or —NE 7 E 8 , or  
       E 5  is —X—(Z) p —Y—E 15    
       wherein 
       X is —O—or —N(E 16 )-,  
       Y is —O—or —N(E 17 )-,  
       Z is C 2 -C 12 -alkylene, C 4 -C 12 -alkylene interrupted by one to three nitrogen atoms, oxygen atoms or a mixture thereof, or is C 3 -C 12 -alkylene, butenylene, butynylene, cyclohexylene or phenylene, each substituted by a hydroxyl group,  
       m is 0, 1, 2 or 3,  
       p is 1, or p is also zero when X and Y are —N(E 16 )— and —N(E 17 )—, respectively,  
       E 15  is a group —CO—C(E 18 )═C(H)E 19  or, when Y is —N(E 17 )—, forms together with E 17  a group —CO—CH═CH—CO—, wherein E 18  is hydrogen or methyl, and E 19  is hydrogen, methyl or —CO—X—E 20,  wherein E 20  is hydrogen, C 1 -C 12 -alkyl or a group of the formula                    
     
     
       5. A composition according to  claim 1  wherein component (b) is a compound of formula IV                    
       wherein 
       G 6  is —CF 3 ,  
       G 7  is hydrogen or —CF 3 ,  
       E 2  and E 2 ′ are independently straight or branched alkyl chain of 1 to 24 carbon atoms. straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms; and  
       L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms, benzylidene, p-xylylene, α,α,α′,α′-tetramethyl-m-xylylene or cycloalkylidene.  
     
     
       6. A composition according to  claim 1  wherein component (b) is a compound of formula I                    
       wherein 
       G 1  is hydrogen,  
       G 2  is —CF 3 ,  
       E 1  is phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms,  
       E 2  is straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms; or E 2  is said alkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more —OH, —OCOE 11 , —NH 2  or —NHCOE 11 , or mixtures thereof, or said alkyl or said alkenyl interrupted by one or more —O— and which can be unsubstituted or substituted by one or more —OH, or is a compound of formula I wherein,  
       G 1  is hydrogen,  
       G 2  is —CF 3 ,  
       E 1  is hydrogen, straight or branched alkyl of 4 to 24 carbon atoms or phenylalkyl of 7 to 15 carbon atoms, and  
       E 2  is as defined above.  
     
     
       7. A composition according to  claim 1  wherein component (b) is a compound of formula IIIA                    
       wherein 
       G 1  is hydrogen,  
       G 2  is —CF 3 ,  
       E 1  is hydrogen, straight or branched alkyl of 4 to 24 carbon atoms or phenylalkyl of 7 to 15 carbon atoms,  
       E 5  is —OE 6  or —NE 7 E 8  where  
       E 6  is hydrogen, straight or branched chain C 1 -C 24 alkyl which is unsubstituted or substituted by one or more OH groups, or —OE 6  is —(OCH 2 CH 2 ) w OH or —(OCH 2 CH 2 ) w OE 21 where w is 1 to 12 and E 21  is alkyl of 1 to 12 carbon atoms, and  
       E 7  and E 8  are independently hydrogen, alkyl of 1 to 18 carbon atoms, straight or branched chain C 3 -C 18 alkyl which is interrupted by —O—, —S— or —NE 11 —, C 5 -C 12 cycloalkyl, C 6 -C 14 aryl or C 1 -C 3 hydroxylalkyl, or E 7  and E 8  together with the N atom are a pyrrolidine, piperidine, piperazine or morpholine ring.  
     
     
       8. A composition according to  claim 1  wherein component (b) is a compound of formula IV                    
       wherein 
       G 6  is —CF 3 ,  
       G 7  is hydrogen or —CF 3 ,  
       E 2  and E 2 ′ are independently straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms; and  
       L is methylene.  
     
     
       9. A composition according to  claim 1  wherein component (b) is 
       (a) 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;  
       (b) 5-trifluoromethyl-2-( 2- hydroxy-5-tert-octylphenyl)-2H-benzotriazole;  
       (c) 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;  
       (d) 2,2′-methylene-bis[6-(5-trifluoromethyl-2H-benzotriazol-2-yl)-4-tert-octylphenol];  
       (e) methylene-2-[4-tert-octyl-6-(2H-benzotriazol-2-yl)phenol]2′-[4-tert-octyl-6-(5-trifluoro-methyl-2H-benzotriazol-2-yl)phenol];  
       (f) 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamic acid;  
       (g) methyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxy-hydrocinnamate;  
       (h) isooctyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxy-hydrocinnamate;  
       (i) 5-trifluoromethyl-2-[2-hydroxy-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;  
       (j) 5-trifluoromethyl-2-[2-hydroxy-5-(3-acryloyloxypropyl)phenyl]-2H-benzotriazole;  
       (k) 5-trifluoromethyl-2-[2-hydroxy-5-(3-methacryloyloxypropyl)phenyl]-2H-benzotriazole;  
       (l) 5-trifluoromethyl-2-[2-hydroxy-5-(3-acrylylaminopropyl)phenyl]-2H-benzotriazole;  
       (m) 5-trifluoromethyl-2-[2-hydroxy-5-(3-methacrylylaminopropyl)phenyl]-2H-benzotriazole;  
       (n) 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-butylphenyl)-2H-benzotriazole;  
       (o) 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-nonylphenyl)-2H-benzotriazole;  
       (p) 5-trifluoromethyl-2-[2-hydroxy-3-α-cumyl-5-(2-hydroxyethyl)phenyl]-2H-benzo- triazole;  
       (q) 5-trifluoromethyl-2-[2-hydroxy-3-α-cumyl-5-(3-hydroxypropyl)phenyl]-2H-benzo- triazole;  
       (r) 5-trifluoromethyl-2-(2-hydroxy-3,5-ditert-amylphenyl)-2H-benzotriazole;  
       (s) 5-trifluoromethyl-2-(2-hydroxy-3,5-ditert-butylphenyl)-2H-benzotriazole;  
       (t) 5-trifluoromethyl-2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole;  
       (u) 5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-hydroxypropyl)phenyl)-2H-benzotriazole;  
       (v) 5-trifluoromethyl-2-(2-hydroxy-3-tert-butyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;  
       (w) 5-trifluoromethyl-2-[2-hydroxy-5-(2-hydroxyethyl)phenyl]-2H-benzotnazole;  
       (x) 5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole; or  
       (y) 5-fluoro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole.  
     
     
       10. A composition according to  claim 1  which additionally contains an effective stabilizing amount of at least one other UV absorber selected from the group consisting the benzotriazoles, the s-triazines, hydroxy-benzophenones, the α-cyanoacrylates, the oxanilides and benzoates. 
     
     
       11. A composition according to  claim 10  wherein the other benzotriazole is selected from the group consisting of 
       2-(2-hydroxy-5-methylphenyl)-2H -benzotriazole;  
       2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;  
       2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole;  
       2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;  
       5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;  
       5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole;  
       2-(2-hydroxy-3-sec-butyl-5-tert-butylphenyl)-2H-benzotriazole;  
       2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole;  
       2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole;  
       2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;  
       2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole;  
       2-[2-hydroxy- 3,(α,α-dimethylbenzyl)- 5-tert-octylphenyl]-2H-benzotriazole;  
       2-{2-hydroxy-3-tert-butyl-5-[2-omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]phenyl}-2H-benzotriazole; and  
       2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H- benzotriazole.  
     
     
       12. A composition according to  claim 11  wherein the other benzotriazole is 
       2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;  
       2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole;  
       2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole;  
       2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]phenyl}-2H-benzotriazole;  
       5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;  
       5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole;  
       2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole; or  
       2-{2-hydroxy-3-tert-butyl-5-(2-(octyloxy)carbonyl)ethyl]phenyl}-2H- benzotriazole.  
     
     
       13. A composition according to  claim 1  which also contains an effective stabilizing amount of a hindered amine.